We report a new series of lipid-based biocompatible ionic liquids (LBILs) consisting of the long-chain phosphonium compound 1,2-dimyristoyl-sn-glycero-3-ethyl-phosphatidylcholine as the cation and the long-chain fatty acids stearic acid, oleic acid, or linoleic acid as anions. These materials were found to be completely miscible with many polar and nonpolar organic solvents as well as dispersible in water. These LBILs also exhibited excellent biocompatibility with an artificial three-dimensional human epidermis model.
Recently, a great attention has been paid to advanced microwave technology that can be used to markedly enhance the biodiesel production process. Ceiba pentandra Seed Oil containing high free fatty acids (FFA) was utilized as a non-edible feedstock for biodiesel production. Microwave-assisted esterification pretreatment was conducted to reduce the FFA content for promoting a high-quality product in the next step. At optimum condition, the conversion was achieved 94.43% using 2wt% of sulfuric acid as catalyst where as 20.83% conversion was attained without catalyst. The kinetics of this esterification reaction was also studied to determine the influence of factors on the rate of reaction and reaction mechanisms. The results indicated that microwave-assisted esterification was of endothermic second-order reaction with the activation energy of 53.717kJ/mol.
Paclitaxel (PTX) injection (i.e., Taxol) has been used as an effective chemotherapeutic treatment for various cancers. However, the current Taxol formulation contains Cremophor EL, which causes hypersensitivity reactions during intravenous administration and precipitation by aqueous dilution. This communication reports the preliminary results on the ionic liquid (IL)-based PTX formulations developed to address the aforementioned issues. The formulations were composed of PTX/cholinium amino acid ILs/ethanol/Tween-80/water. A significant enhancement in the solubility of PTX was observed with considerable correlation with the density and viscosity of the ILs, and with the side chain of the amino acids used as anions in the ILs. Moreover, the formulations were stable for up to 3 months. The driving force for the stability of the formulation was hypothesized to be the involvement of different types of interactions between the IL and PTX. In vitro cytotoxicity and antitumor activity of the IL-based formulations were evaluated on HeLa cells. The IL vehicles without PTX were found to be less cytotoxic than Taxol, while both the IL-based PTX formulation and Taxol exhibited similar antitumor activity. Finally, in vitro hypersensitivity reactions were evaluated on THP-1 cells and found to be significantly lower with the IL-based formulation than Taxol. This study demonstrated that specially designed ILs could provide a potentially safer alternative to Cremophor EL as an effective PTX formulation for cancer treatment giving fewer hypersensitivity reactions.
Herein, we report ethosome (ET) formulations composed of a safe amount of 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC)-based ionic liquid with various concentrations of ethanol as a carrier for the transdermal delivery of a high molecular weight drug, insulin. The Insulin-loaded ET vesicles exhibited long-term stability compared to conventional DMPC ETs, showing significantly higher drug encapsulation efficiency and increased skin permeation ability.
The well-known toxicity of conventional chemical oil spill dispersants demands the development of alternative and environmentally friendly dispersant formulations. Therefore, in the present study we have developed a pair of less toxic and green dispersants by combining lactonic sophorolipid (LS) biosurfactant individually with choline myristate and choline oleate ionic liquid surfactants. The aggregation behavior of resulted surfactant blends and their dispersion effectiveness was investigated using the baffled flask test. The introduction of long hydrophobic alkyl chain with unsaturation (attached to choline cation) provided synergistic interactions between the binary surfactant mixtures. The maximum dispersion effectiveness was found to be 78.23% for 80:20 (w/w) lactonic sophorolipid-choline myristate blends, and 81.15% for 70:30 (w/w) lactonic sophorolipid-choline oleate blends at the dispersant-to-oil ratio of 1:25 (v/v). The high dispersion effectiveness of lactonic sophorolipid-choline oleate between two developed blends is attributed to the stronger synergistic interactions between surfactants and slower desorption rate of blend from oil-water interface. The distribution of dispersed oil droplets at several DOR were evaluated and it was observed that oil droplets become smaller with increasing DOR. In addition, the acute toxicity analysis of developed formulations against zebra fish (Danio rerio) confirmed their non-toxic behavior with LC50 values higher than 400 ppm after 96 h. Overall, the proposed new blends/formulations could effectively substitute the toxic and unsafe chemical dispersants.
In the present investigation, a total of 108 combinations of ionic liquids (ILs) were screened using the conductor-like screening model for real solvents (COSMO-RS) with the aid of six cations and eighteen anions for the extraction of succinic acid (SA) from aqueous streams through dispersive liquid-liquid microextraction (DLLME). Using the screened ILs, an ionic liquid-based DLLME (IL-DLLME) was developed to extract SA and the role of different reaction parameters in the effectiveness of IL-DLLME approach was investigated. COSMO-RS results suggested that, quaternary ammonium and choline cations form effective IL combinations with [OH¯], [F¯], and [SO42¯] anions due to hydrogen bonding. In view of these results, one of the screened ILs, tetramethylammonium hydroxide [TMAm][OH] was chosen as the extractant in IL-DLLME process and acetonitrile was adopted as the dispersive solvent. The highest SA removal efficiency of 97.8% was achieved using 25 μL of IL [TMAm][OH] as a carrier and 500 μL of acetonitrile as dispersive solvent. The highest amount of SA was extracted with a stir time of 20 min at 300 rpm, followed by centrifugation for 5 min at 4500 rpm. Overall, the findings showed that IL-DLLME is efficient in extracting succinic acid from aqueous environments while adhering to the first-order kinetics.
The transdermal delivery of sparingly soluble drugs is challenging due to of the need for a drug carrier. In the past few decades, ionic liquid (IL)-in-oil microemulsions (IL/O MEs) have been developed as potential carriers. By focusing on biocompatibility, we report on an IL/O ME that is designed to enhance the solubility and transdermal delivery of the sparingly soluble drug, acyclovir. The prepared MEs were composed of a hydrophilic IL (choline formate, choline lactate, or choline propionate) as the non-aqueous polar phase and a surface-active IL (choline oleate) as the surfactant in combination with sorbitan laurate in a continuous oil phase. The selected ILs were all biologically active ions. Optimized pseudo ternary phase diagrams indicated the MEs formed thermodynamically stable, spherically shaped, and nano-sized (<100 nm) droplets. An in vitro drug permeation study, using pig skin, showed the significantly enhanced permeation of acyclovir using the ME. A Fourier transform infrared spectroscopy study showed a reduction of the skin barrier function with the ME. Finally, a skin irritation study showed a high cell survival rate (>90%) with the ME compared with Dulbecco's phosphate-buffered saline, indicates the biocompatibility of the ME. Therefore, we conclude that IL/O ME may be a promising nano-carrier for the transdermal delivery of sparingly soluble drugs.
Ibuprofen (Ibf) is a biologically active drug (BADs) and an emerging contaminant of concern (CECs) in aqueous streams. Due to its adverse effects upon aquatic organisms and humans, the removal and recovery of Ibf are essential. Usually, conventional solvents are employed for the separation and recovery of ibuprofen. Due to environmental limitations, alternative green extracting agents need to be explored. Ionic liquids (ILs), emerging and greener alternatives, can also serve this purpose. It is essential to explore ILs that are effective for recovering ibuprofen, among millions of ILs. The conductor-like screening model for real solvents (COSMO-RS) is an efficient tool that can be used to screen ILs specifically for ibuprofen extraction. The main objective of this work was to identify the best IL for the extraction of ibuprofen. A total of 152 different cation-anion combinations consisting of eight aromatic and non-aromatic cations and nineteen anions were screened. The evaluation was based upon activity coefficients, capacity, and selectivity values. Furthermore, the effect of alkyl chain length was studied. The results suggest that quaternary ammonium (cation) and sulfate (anion) have better extraction ability for ibuprofen than the other combinations tested. An ionic liquid-based green emulsion liquid membrane (ILGELM) was developed using the selected ionic liquid as the extractant, sunflower oil as the diluent, Span 80 as the surfactant, and NaOH as the stripping agent. Experimental verification was carried out using the ILGELM. The experimental results indicated that the predicted COSMO-RS and the experimental results were in good agreement. The proposed IL-based GELM is highly effective for the removal and recovery of ibuprofen.
Ionic liquids (ILs), a potentially attractive "green," recyclable alternative to environmentally harmful volatile organic compounds, have been increasingly exploited as solvents and/or cosolvents and/or reagents in a wide range of applications, including pretreatment of lignocellulosic biomass for further processing. The enzymatic delignification of biomass to degrade lignin, a complex aromatic polymer, has received much attention as an environmentally friendly process for clean separation of biopolymers including cellulose and lignin. For this purpose, enzymes are generally isolated from naturally occurring fungi or genetically engineered fungi and used in an aqueous medium. However, enzymatic delignification has been found to be very slow in these conditions, sometimes taking several months for completion. In this chapter, we highlight an environmentally friendly and efficient approach for enzymatic delignification of lignocellulosic biomass using room temperature ionic liquids (ILs) as (co)solvents or/and pretreatment agents. The method comprises pretreatment of lignocellulosic biomass in IL-aqueous systems before enzymatic delignification, with the aim of overcoming the low delignification efficiency associated with low enzyme accessibility to the solid substrate and low substrate and product solubilities in aqueous systems. We believe the processes described here can play an important role in the conversion of lignocellulosic biomass-the most abundant renewable biomaterial in the world-to biomaterials, biopolymers, biofuels, bioplastics, and hydrocarbons. Graphical Abstract.
Since injection administration for diabetes is invasive, it is important to develop an effective transdermal method for insulin. However, transdermal delivery remains challenging owing to the strong barrier function of the stratum corneum (SC) of the skin. Here, we developed ionic liquid (IL)-in-oil microemulsion formulations (MEFs) for transdermal insulin delivery using choline-fatty acids ([Chl][FAs])-comprising three different FAs (C18:0, C18:1, and C18:2)-as biocompatible surface-active ILs (SAILs). The MEFs were successfully developed using [Chl][FAs] as surfactants, sorbitan monolaurate (Span-20) as a cosurfactant, choline propionate IL as an internal polar phase, and isopropyl myristate as a continuous oil phase. Ternary phase behavior, dynamic light scattering, and transmission electron microscopy studies revealed that MEFs were thermodynamically stable with nanoparticle size. The MEFs significantly enhanced the transdermal permeation of insulin via the intercellular route by compromising the tight lamellar structure of SC lipids through a fluidity-enhancing mechanism. In vivo transdermal administration of low insulin doses (50 IU/kg) to diabetic mice showed that MEFs reduced blood glucose levels (BGLs) significantly compared with a commercial surfactant-based formulation by increasing the bioavailability of insulin in the systemic circulation and sustained the insulin level for a much longer period (half-life > 24 h) than subcutaneous injection (half-life 1.32 h). When [Chl][C18:2] SAIL-based MEF was transdermally administered, it reduced the BGL by 56% of its initial value. The MEFs were biocompatible and nontoxic (cell viability > 90%). They remained stable at room temperature for 3 months and their biological activity was retained for 4 months at 4 °C. We believe SAIL-based MEFs will alter current approaches to insulin therapy and may be a potential transdermal nanocarrier for protein and peptide delivery.
An inductively tuned modified split-ring resonator-based metamaterial (MTM) is presented in this article that provides multiple resonances covering S, C, X, and Ku-bands. The MTM is designed on an FR-4 substrate with a thickness of 1.5 mm and an electrical dimension of 0.063λ × 0.063λ where wavelength, λ is calculated at 2.38 GHz. The resonator part is a combination of three squared copper rings and one circular ring in which all the square rings are modified shaped, and the inner two rings are interconnected. The resonance frequency is tuned by adding inductive metal strips in parallel two vertical splits of the outer ring that causes a significant shift of resonances towards the lower frequencies and a highly effective medium ratio (EMR) of 15.75. Numerical simulation software CST microwave studio is used for the simulation and performance analysis of the proposed unit cell. The MTM unit cell exhibits six resonances of transmission coefficient (S21) at 2.38, 4.24, 5.98, 9.55, 12.1, and 14.34 GHz covering S, C, X, and Ku-bands with epsilon negative (ENG), near-zero permeability, and near-zero refractive index (NZI). The simulated result is validated by experiment with good agreement between them. The performance of the array of the unit cells is also investigated in both simulation and measurement. The equivalent circuit modeling has been accomplished using Advanced Design Software (ADS) that shows a similar S21 response compared to CST simulation. Noteworthy to mention that with the copper backplane, the same unit cell provides multiband absorption properties with four major absorption peaks of 99.6%, 95.7%, 99.9%, 92.7% with quality factors(Q-factor) of 28.4, 34.4, 23, and 32 at 3.98, 5.5, 11.73 and 13.47 GHz, respectively which can be applied for sensing and detecting purposes. The application of an array of the unit cells is investigated using it as a superstrate of an antenna that provides a 73% (average) increase of antenna gain. Due to its simple design, compact dimension with high EMR, ENG property with near-zero permeability, this multiband NZI metamaterial can be used for microwave applications, especially for multiband antenna gain enhancement.
In order to prevent common hypersensitivity reactions to paclitaxel injections (Taxol), we previously reported an ionic liquid-mediated paclitaxel (IL-PTX) formulation with small particle size and narrow size distribution. The preliminary work showed high PTX solubility in the IL, and the formulation demonstrated similar antitumor activity to Taxol, while inducing a smaller hypersensitivity effect in in vitro cell experiments. In this study, the stability of the IL-PTX formulation was monitored by quantitative HPLC analysis, which showed that IL-PTX was more stable at 4 °C than at room temperature. The in vivo study showed that the IL-PTX formulation could be used in a therapeutic application as a biocompatible component of a drug delivery system. To assess the in-vivo biocompatibility, IL or IL-mediated formulations were administered intravenously by maintaining physiological buffered conditions (neutral pH and isotonic salt concentration). From in vivo pharmacokinetics data, the IL-PTX formulation was found to have a similar systemic circulation time and slower elimination rate compared to cremophor EL mediated paclitaxel (CrEL-PTX). Furthermore, in vivo antitumor and hypersensitivity experiments in C57BL/6 mice revealed that IL-PTX had similar antitumor activity to CrEL-PTX, but a significantly smaller hypersensitivity effect compared with CrEL-PTX. Therefore, the IL-mediated formulation has potential to be an effective and safe drug delivery system for PTX.
The aim of the present study was to characterize the phenolic acids, flavonoids, and antioxidant properties of monofloral honey collected from five different districts in Bangladesh. A new high performance liquid chromatography (HPLC) equipped with a UV detector method was developed for the identification of the phenolic acids and flavonoids. A total of five different phenolic acids were identified, with the most abundant being caffeic acid, benzoic acid, gallic acid, followed by chlorogenic acid and trans-cinnamic acid. The flavonoids, kaempferol, and catechin were most abundant, followed by myricetin and naringenin. The mean moisture content, total sugar content, and color characteristics of the honey samples were 18.36 ± 0.95%, 67.40 ± 5.63 g/100 g, and 129.27 ± 34.66 mm Pfund, respectively. The mean total phenolic acids, total flavonoid content, and proline content were 199.20 ± 135.23, 46.73 ± 34.16, and 556.40 ± 376.86 mg/kg, respectively, while the mean FRAP values and DPPH radical scavenging activity were 327.30 ± 231.87 μM Fe (II)/100 g and 36.95 ± 20.53%, respectively. Among the different types of honey, kalijira exhibited the highest phenolics and antioxidant properties. Overall, our study confirms that all the investigated honey samples are good sources of phenolic acids and flavonoids with good antioxidant properties.
Withania somnifera is an important medicinal plant traditionally used in the treatment of many diseases. The present study was carried out to characterize the phenolic acids, flavonoids and 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) scavenging activities in methanolic extracts of W. somnifera fruits, roots and leaves (WSFEt, WSREt and WSLEt).
The present study was undertaken to determine the heavy metal levels and the physicochemical parameters (pH, electrical conductivity (EC), and ash, moisture, and total sugar content) of honeys from Bangladesh. Three different floral honeys were investigated, namely, khalsi (Aegiceras corniculatum), mustard (Brassica juncea), and litchi (Litchi chinensis) honeys. The heavy metals in the honeys were determined by using a High Temperature Dry Oxidation method followed by Atomic Absorption Spectroscopy. The mean pH, EC, and ash, moisture, and total sugar contents of the investigated honeys were 3.6, 0.51 mS/cm, 0.18%, 18.83%, and 68.30%, respectively. Iron was the most abundant among all the investigated heavy metals, ranging from 13.51 to 15.44 mg/kg. The mean concentrations of Mn and Zn in the investigated honeys were 0.28 mg/kg and 2.99 mg/kg, respectively. Cd was below the detection limit, and lead was found in some honey samples, but their contents were below the recommended Maximum Acceptable Level. Cr was also found in all of the samples, but its concentration was within the limit. The physicochemical analysis of the honey samples yielded levels within the limits set by the international honey legislation, indicating that the honey samples were of good quality and had acceptable values for maturity, purity, and freshness.
In this article, a unique metamaterial (MTM) structure is presented that exhibits four resonances of transmission coefficient (S21) that fall into S, X, and Ku bands. The MTM design is initiated on a Rogers (RT5880) substrate with an electrical dimension of 0.088 λ × 0.088 λ (λ is calculated at 3.424 GHz). The resonating patch contains four quartiles connected by a central metallic strip. The placement of each quartile is such that the whole resonator is mirror symmetric about the vertical axis. Two H-shaped modifiers connect two quartiles of each vertical half of the resonator. These H-shaped modifiers form the resonance cavity in its vicinity, and thus help significantly to orient the overall resonances of the proposed MTM at 3.424 GHz, 10 GHz, 14.816 GHz, and 16.848 GHz. The resonance phenomena are examined through equivalent circuit modeling and verified in Advanced Design Software (ADS). Metamaterial properties of the proposed MTM are extracted and it exhibits negative permittivity, permeability, and refractive index. The prototype of the MTM is fabricated and measurement is taken. The measured S21 shows a close similarity with the simulated result. Moreover, effective medium ratio (EMR) is calculated for the proposed MTM and a high EMR of 10.95 is obtained that expresses its compactness. This compact MTM with negative permittivity, permittivity, and refractive index can be important component for improving the performance of the miniaturized devices for multi-band wireless communication systems.
Glycerol pretreatment is a promising method for the environmentally-friendly transformation of lignocellulosic materials into sustainable cellulose-rich raw materials (i.e., biopolymer) to fabricate biocomposites. Here, a comparison of aqueous acidified glycerol (AAG) pretreatment of wheat straw (WS) with alkaline, hot water, and dilute acid pretreatments on the thermal and mechanical characteristics of their fabricated composite board is presented. A comparison of total energy expenditure during WS pretreatment with AAG and other solutions was estimated and a comparative influence of AAG processing on lignocellulosic constituents and thermal stability of WS fiber was studied. Results imply that AAG pretreatment was superior in generating cellulose-rich fiber (CRF) as compared to other pretreatments and enhanced the cellulose contents by 90% compared to raw WS fiber. Flexural strength of acidic (40.50 MPa) and hot water treated WS composite (38.71 MPa) was higher compared to the value of 33.57 MPa for untreated composite, but AAG-treated composites exhibited lower values of flexural strength (22.22 MPa) compared to untreated composite samples. Conversely, AAG pretreatment consumed about 56% lesser energy for each kg of WS processed as compared to other pretreatments. These findings recognize that glycerol pretreatment could be a clean and new pretreatment strategy to convert agricultural waste into high-quality CRF as a sustainable raw material source for engineered biocomposite panels.
This study was conducted to evaluate the effects of evaporation, gamma irradiation and temperature on the total polyphenols, flavonoids and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging activities of Tualang honey samples (n = 14) following storage over three, six or twelve months. The mean polyphenol concentrations of the six gamma irradiated honey samples at three, six and twelve months, respectively, were 96.13%, 98.01% and 102.03% higher than the corresponding values of the eight non-gamma irradiated samples. Similarly, the mean values for flavonoids at three, six and twelve months were 111.52%, 114.81% and 110.04% higher, respectively, for the gamma irradiated samples. The mean values for DPPH radical-scavenging activities at three, six and twelve months were also 67.09%, 65.26% and 44.65% higher, respectively, for the gamma irradiated samples. These data indicate that all gamma irradiated honey samples had higher antioxidant potential following gamma irradiation, while evaporation and temperature had minor effects on antioxidant potential.
Flavonoids have diverse beneficial roles that potentiate their application as nutraceutical agents in nutritional supplements and as natural antimicrobial agents in food preservation. To address poor solubility and bioactivity issues, we developed water-soluble micellar formulations loaded with single and multiple flavonoids using the biocompatible surface-active ionic liquid choline oleate. The food preservation performance was investigated using luteolin, naringenin, and quercetin as model bioactive compounds. The micellar formulations formed spherical micelles with particle sizes of <150 nm and exhibited high aqueous solubility (>5.15 mg/mL). Co-delivery of multiple flavonoids (luteolin, naringenin, and quercetin in LNQ-MF) resulted in 84.85% antioxidant activity at 100 μg/mL. The effects on Staphylococcus aureus and Salmonella enterica were synergistic with fractional inhibitory concentration indices of 0.87 and 0.71, respectively. LNQ-MF hindered the growth of S. aureus in milk (0.83-0.89 log scale) compared to the control. Co-delivered encapsulated flavonoids are a promising alternative to chemical preservatives.
Nitrogen loss from urea fertiliser due to its high solubility characteristics has led to the invention of controlled release urea (CRU). Majority of existing CRU coatings are produced from a non-biodegradable, toxic and expensive synthetic polymers. This study determines the feasibility of fly ash-based geopolymer as a coating material for urea fertilizer. The effects of fly ash particle size (15.2 μm, 12.0 μm, and 8.6 μm) and solid to liquid (S : L) ratio (3 : 1, 2.8 : 1, 2.6 : 1, 2.4 : 1 and 2.2 : 1) on the geopolymer coating, the characterization such as FTIR analysis, XRD analysis, surface area and pore size analysis, setting time analysis, coating thickness, and crushing strength, and the release kinetics of geopolymer coated urea in water and soil were determined. Lower S : L ratio was beneficial in terms of workability, but it had an adverse impact on geopolymer properties where it increased porosity and decreased mechanical strength to an undesirable level for the CRU application. Geopolymer coated urea prepared from the finest fly ash fraction and lowest S : L ratio demonstrated high mechanical strength and slower urea release profile. Complete urea release was obtained in 132 minutes in water and 15 days in soil from geopolymer-coated urea whereas for uncoated urea it took only 20 minutes in water and 3 days in soil. Thus, geopolymer can potentially be used as a coating material for urea fertilizer to replace commonly used expensive and biodegradable polymer-based coatings.